CN104610957B - Europium luminous polyester fiber and preparation method thereof - Google Patents
Europium luminous polyester fiber and preparation method thereof Download PDFInfo
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- CN104610957B CN104610957B CN201510044704.3A CN201510044704A CN104610957B CN 104610957 B CN104610957 B CN 104610957B CN 201510044704 A CN201510044704 A CN 201510044704A CN 104610957 B CN104610957 B CN 104610957B
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- 239000000835 fiber Substances 0.000 title claims abstract description 65
- 229910052693 Europium Inorganic materials 0.000 title claims abstract description 60
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 229920000728 polyester Polymers 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 72
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000009987 spinning Methods 0.000 claims abstract description 18
- 239000003446 ligand Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000007935 neutral effect Effects 0.000 claims abstract description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 115
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- 235000019441 ethanol Nutrition 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 15
- 238000000967 suction filtration Methods 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 14
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005292 vacuum distillation Methods 0.000 claims description 12
- OXQOBQJCDNLAPO-UHFFFAOYSA-N 2,3-Dimethylpyrazine Chemical class CC1=NC=CN=C1C OXQOBQJCDNLAPO-UHFFFAOYSA-N 0.000 claims description 10
- 230000001476 alcoholic effect Effects 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 238000002074 melt spinning Methods 0.000 claims description 8
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Inorganic materials [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- CFLWIVMDYUDICT-UHFFFAOYSA-N 4,4,4-trifluoro-3-oxobutanal Chemical compound FC(F)(F)C(=O)CC=O CFLWIVMDYUDICT-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 230000003068 static effect Effects 0.000 claims description 5
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000004020 luminiscence type Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 230000001186 cumulative effect Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 238000005215 recombination Methods 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 238000000638 solvent extraction Methods 0.000 claims description 3
- 230000006798 recombination Effects 0.000 claims description 2
- 238000010583 slow cooling Methods 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 41
- 150000002910 rare earth metals Chemical class 0.000 abstract description 36
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 28
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 28
- 239000002131 composite material Substances 0.000 abstract description 14
- 230000005284 excitation Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- OWDZQVCOYJZNGC-UHFFFAOYSA-N thiophene 4,4,4-trifluoro-3-oxobutanal Chemical class FC(C(=O)CC=O)(F)F.S1C=CC=C1 OWDZQVCOYJZNGC-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 51
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 238000005422 blasting Methods 0.000 description 6
- 125000005909 ethyl alcohol group Chemical group 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000010041 electrostatic spinning Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- 238000000018 DNA microarray Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- WHLUQAYNVOGZST-UHFFFAOYSA-N tifenamil Chemical group C=1C=CC=CC=1C(C(=O)SCCN(CC)CC)C1=CC=CC=C1 WHLUQAYNVOGZST-UHFFFAOYSA-N 0.000 description 2
- QUDYTXLAVSMKEF-UHFFFAOYSA-N CCC(C)[U]/C(/C(F)(F)F)=C\C(\c1ccc[s]1)=[O]/C Chemical compound CCC(C)[U]/C(/C(F)(F)F)=C\C(\c1ccc[s]1)=[O]/C QUDYTXLAVSMKEF-UHFFFAOYSA-N 0.000 description 1
- 229910016644 EuCl3 Inorganic materials 0.000 description 1
- 101000679359 Homo sapiens Phosphatidylinositol 3,4,5-trisphosphate 3-phosphatase TPTE2 Proteins 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- TXBBUSUXYMIVOS-UHFFFAOYSA-N O=C(CC(c1ccc[s]1)=O)C(F)(F)F Chemical compound O=C(CC(c1ccc[s]1)=O)C(F)(F)F TXBBUSUXYMIVOS-UHFFFAOYSA-N 0.000 description 1
- 102100022577 Phosphatidylinositol 3,4,5-trisphosphate 3-phosphatase TPTE2 Human genes 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004595 color masterbatch Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- LNBHUCHAFZUEGJ-UHFFFAOYSA-N europium(3+) Chemical group [Eu+3] LNBHUCHAFZUEGJ-UHFFFAOYSA-N 0.000 description 1
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000000990 laser dye Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 230000005311 nuclear magnetism Effects 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
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- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- 238000010791 quenching Methods 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention discloses a kind of Europium luminous polyester fiber and preparation method thereof, a kind of Phen neutral ligand is prepared first and is coordinated with reference to α thiophene trifluoro formyl acetones with rare earth Eu (III), titrated using first normal pressure, the method for rear reaction under high pressure prepares the Rare Earth Europium Complex Eu (TTA) close to nanoscale3DMPaPhen luminescent materials.The material is 10 in concentration‑5Mol/L CH2Cl2Launch very strong pure feux rouges in solution, at 615nm.Composite molten spinning is carried out as luminescent material and polyethylene terephthalate (PET) using this complex and prepares luminescent fibre.It is 10 in concentration when content is 0.05% to rare earth luminescent material in the fibre‑5Launch stronger pure feux rouges in mol/L DMF solution, luminous position is still at 615nm.The luminescent fibre has excitation height, the preferable advantage of spinnability.
Description
Technical field
The invention belongs to luminescent material and textile science field, more particularly to a kind of Europium luminous polyester fiber and its system
Preparation Method.
Background technology
Rare earth element is located at group of the lanthanides in the periodic table of elements, because its outer electronic structure is identical, and internal layer 4f energy level ratios
More close, rare earth element shows the physics and chemical property of many uniquenesses, so being used widely in light, electricity, magnetic field.
The fluorescent emission of general rare earth ion mostlys come from the f-f electron transitions of 4f electronic shell, 5S2And 5P6Electronics typically can be 4f electricity
Son is shielded, therefore light radiation transition influence of the matrix on 4f electronic shell is smaller.This shielding action can exactly make rare earth from
Son produces sharp band transmitting and longer fluorescence lifetime.
Usual most of less molar extinction coefficients of trivalent rare earth ionses, make the fluorescence intensity and not bery by force of its own,
When its fluorescence intensity can be strengthened after organic ligand and rare-earth ion coordination, here it is " antenna " effect.Rare earth compounding is used as hair
There are several clear advantages in stimulative substance：(a) luminous efficiency is high：The highest luminous efficiency of organic molecule is 25% in theory, and
Rare earth compounding is theoretical up to 100%；(b) photochromic purity is high：The luminous of rare earth compounding is produced by the f-f transition of central ion
Raw, its spectral bands is very narrow, emission spectrum half peak breadth (<10nm)；(c) modified ligand does not influence glow color：Rare earth is matched somebody with somebody
The emission spectrum of compound is different from the emission spectrum of general transient metal complex, typically in order to improve the easy processing of complex
The properties such as the migration of property, solubility, charge migration and carrier, often will be modified part to meet above-mentioned requirements.
These advantages are widely used to the fields such as phosphor, fluorescent lamp, laser dye, the electroluminescent material of color monitor.
It is of interest that Eu (III) complexs have obtained researcher as the excellent photic or red electroluminescent phosphor material of a class.Grind
A key point for studying carefully Eu (III) complex is the design and optimization to part, and the hair of complex is influenceed by the change of part
The required voltage of light efficiency, stability and device, therefore the change of part has far-reaching influence to the performance of material.Document
(Noto M, Irie K, Era M.Chem.Lett, 2011,320) is prepared for a Rare Earth Europium Complex luminescent material Eu (L)3Phen solid fluorescences efficiency is 50%.Document (Sun M, Xin H, Wang, et al.Chem.Commun, 2003,702) is in
Property part on introduce cavity transmission group triphenylamine, to adjust electronics and hole transmission, prepared luminescent material Eu
(DBM)3(TPIP) good fluorescent effect is obtained, the device brightness of assembling is up to 1305cd/m2, maximum fluorescence yield is
1.44lm/W.Document (Ling Q.D, Cai Q.J, Huang W et al.Mater Chem, 2004,14,2741-2746) is made
For side chain type macromolecule rare-earth europium luminescent material, it is polymerize using the hole transporting property of carbazole with emitting complexes, but
This kind of material carries side chain, and molecular weight hardly possible control during polymerization, it is difficult to which directly carrying out spinning prepares luminescent fibre.
The preparation of luminescent fibre is usually that luminescent material is doped in high polymer, and luminescent fibre is made through spinning.Its
Method is roughly divided into：Solution-polymerized SBR, melt spinning, face coat etc..Solution-polymerized SBR requires that luminescent material can be dissolved in solvent, melts
Melt spinning requirement fluorescent material stable, heating is not easily decomposed, resistance to oxidation etc., and is shown coating and then required luminescent material and fiber table
There is good affinity in face.
In recent years to the existing relevant report of exploitation of luminescent fibre, some seminars are prepared for one using electrostatic spinning technique
A little rear-earth-doped polymer nanofibers and inorganic nano-fiber.Luo Jun et al. is prepared for series of rare earth silicate long-afterglow
Luminescent material doping carries out electrostatic spinning (China Patent Publication No. in the fibre：CN103938297A, application number：
201410174370.7), this fluorescent fiber can launch indigo plant through visible ray or ultraviolet light 1-10 minutes at 470nm.This
Fiber prepared by class luminescent material has the effect of extinction energy storage, with long-persistence luminous feature；General prepared inorganic silicon
Salt luminescent material increasing particle size, it is poor to be doped to spinnability in fiber, and exists in terms of false proof and electroluminescent and lack
Fall into.Chinese patent CN102251298B, application number：201110150250.X) describe a kind of system of composite Nano luminescent fibre
It is standby, reacted using rare earth compounding or rare earth mixing with nano are brilliant under excusing from death ripple with polymer monomer, generate nucleocapsid structure
Compound, recombination luminescence fiber is then prepared for by electrostatic spinning.Sui X.M. et al. (X.M.Sui, C.L.Shao,
Y.C.Liu et al.Appl.Phys.Lett., 2005,87,113-115) ZnO/PVA composite fibres are prepared for, it can launch white
Coloured light.Eu in document (H.Zhang, H.W.Song, B.Dong et al.J.Phy.Chem, 2008,112,9155-9162)
(BA)3(TPPO)2It is entrained in PVP (Poly Vinyl Pyrrolidone, polyvinylpyrrolidone) and carries out composite spinning, system
Standby bleach-resistant ability is strong, the composite nano fiber of stable luminescence；Due to part and Eu (III) ion level-density parameter situation not
It is fine, the luminous intensity of caused complex is not very high.Chinese patent CN101381901A, application number：
200810042269.0, it is prepared for a series of organic molecule fluorescent chemicalses and is doped in polypropylene to carry out melt spinning, makes
For the polypropylene luminescent fibre for going out good, the different glow colors of luminescent properties；This kind of fiber prepared with pure organic molecule, it is resistance to
Oxidisability, excitation, luminous efficiency and luminous intensity are poor.
The content of the invention
The brief overview on the present invention is given below, to provide the basic reason on certain aspects of the invention
Solution.It should be appreciated that this general introduction is not the exhaustive general introduction on the present invention.It is not intended to determine the key of the present invention
Or pith, nor is it intended to limit the scope of the present invention.Its purpose only provides some concepts in simplified form, with
This is used as the preamble in greater detail discussed later.
The purpose of the embodiment of the present invention be for above-mentioned prior art defect there is provided one kind in ultraviolet light or electroluminescent
Under the conditions of there is the preparation method of the high Europium luminous polyester fiber of efficient, luminous intensity.
To achieve these goals, the present invention is adopted the technical scheme that：
A kind of Europium complex luminescent material, its chemical formula is C24H16EuN4SF3O2, molecular formula is Eu (TTA)3DMPaPhen, wherein TTA are：α-thiophene trifluoro formyl acetone, DMPaPhen are：Simultaneously [1,10] are adjacent luxuriant and rich with fragrance for 2,3- dimethyl pyrazines
Sieve quinoline, structural formula is：
Present invention also offers a kind of preparation method of Europium complex luminescent material, comprise the following steps：
(1) preparation of part 2,3- dimethyl pyrazines simultaneously [1,10] Phen：
A, 1,10- Phens and KBr be put into flask, it is 3 that volume ratio is added dropwise at -8 DEG C to -12 DEG C:1-2's
The mixed acid solution of the concentrated sulfuric acid and concentrated nitric acid, 0.5-1.5h is reacted at -8 DEG C to -12 DEG C, is heated to 75-95 DEG C of reaction 130-
150min；Reaction solution is instilled in ice cube, quick stirring, and pH is adjusted to 6-7 with NaOH, obtains neutralizing solution, with described in solvent extraction
Solution is neutralized, vacuum distillation obtains yellow product 5,6- diketone -1,10- Phens；
B, by 5,6- diketone -1,10- Phens, hydroxylamine hydrochloride and BaCO310- is reacted in 70-80 DEG C of ethanol
13h, distillation, solid is washed with 0.2-0.3mol/L watery hydrochloric acid, and suction filtration is washed for several times with the first mixed liquor, then is dried in vacuo,
Obtain light yellow product 5,6- dioxime -1,10- Phens；
C, 5,6- dioxime -1,10- Phens are put into absolute ethyl alcohol, obtain alcoholic solution, heated under inert gas shielding
To 70-80 DEG C, take sodium hydrosulfite to be dissolved in the ammonia spirit that content is 3%-5%, obtain the second mixed liquor, the second mixed liquor is added
Enter in above-mentioned alcoholic solution；The second mixed liquor with first time equivalent is added after 15-45min, and 1.5- is reacted at 75-85 DEG C
2h；Normal temperature is cooled to, suction filtration is washed for several times for several times, then with ethanol or acetone with distillation water washing, and vacuum drying obtains golden yellow
Color 5,6- diamines -1,10- Phens；
D, 5,6- diamines -1,10- Phen and 3,4- diacetyl react to 10-13h at normal temperatures, vacuum distillation, Gu
Body is washed with the mixed liquor of methanol and water, vacuum drying, obtains white powder 2,3- dimethyl pyrazines simultaneously [1,10] Phen；
(2) organic RE europium complex Eu (TTA)3The preparation of DMPaPhen luminescent materials：
By Eu2O3With concentrated hydrochloric acid mixing, it is evaporated on electric jacket, is then configured to ethanol solution；Take a certain amount of Phen
Neutral ligand DMPaPhen is put into flask, is added dropwise at 55-60 DEG C equimolar with Phen neutral ligand DMPaPhen
EuCl3Ethanol solution, stir 40-80 minutes；Phen neutral ligand DMPaPhen, the HTTA of 3 times of moles is added dropwise
Ethanol solution, adjusts pH to 6-7, is transferred to autoclave, insulation reaction 5-6h with triethylamine；Vacuum distillation, cooling separates out solid, takes out
Filter, alcohol is washed for several times, washed several times with water, vacuum drying, obtains nano level blush powder.
Present invention simultaneously provides a kind of preparation method of Europium luminous polyester fiber, coordinated using the Europium
Thing luminescent material is cut into slices with PET (polyethylene terephthalate, pet resin) and carried out
Blending, then luminous polyester fiber is made through melt spinning.
The present invention provides a kind of Europium luminous polyester fiber again, is prepared according to above-mentioned preparation method.
Compared with prior art, the beneficial effects of the invention are as follows：
1) triplet and Eu (III) ion are prepared5D0The part DMPaPhen that energy level is effectively matched, makes prepared
Luminous efficiency, the luminous intensity of Rare Earth Europium Complex are effectively improved, the heat endurance of complex, oxidative resistance enhancing.It is luminous strong
The raising of degree and efficiency can effectively reduce the addition of complex, break end when reducing spinning, around roller, improve spinnability.
2) larger using complex grain diameter made from synthesis under normal pressure, the present invention is used after normal pressure has titrated part,
Solution is transferred to autoclave insulation reaction again, the complex close to nanoscale can be prepared using solvent heat, is cut into slices with PET
Carry out composite spinning when can reduce broken end, around roller the problems such as.
3) present invention using first prepare luminescent material Masterbatch again with through dry thickening after PET section carry out Compound spinning
Silk, can be such that luminescent material is uniformly dispersed in polymeric system, prevent from producing Fluorescence-quenching under high concentration.
4) present invention is set specific process conditions, can continuously carry out POY (preorientations by melt spinning method
Silk) and UDY (undrawn yarn) spinning, the Europium luminescent fibre that fiber thickness is uniform, strength is appropriate is made.
5) present invention obtains preparation luminous intensity good, dispersed by preparing organic rare-earth ligand luminescent material
The new way for the luminescent fibre that good, chemical stability is high, fiber number is uniform, strength is appropriate.Can false proof, clothes, seabed operation, point
The fields such as sub- probe, biochip, communication, solar cell have important application.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the accompanying drawing used required in technology description to be briefly described, drawings in the following description are only some realities of the present invention
Example is applied, for those of ordinary skill in the art, without having to pay creative labor, can also be attached according to these
Figure obtains other accompanying drawings.
Fig. 1 is organic RE europium complex Eu (TTA)3DMPaPhen synthetic route chart；
Fig. 2 is Rare Earth Europium Complex Eu (TTA) prepared by the inventive method3DMPaPhen's and part DMPaPhen is infrared
Spectrogram, wherein a are Eu (TTA)3DMPaPhen, b are DMPaPhen；
Fig. 3 is Rare Earth Europium Complex Eu (TTA) prepared by the inventive method3DMPaPhen nuclear magnetic spectrogram；
Fig. 4 is Rare Earth Europium Complex Eu (TTA) prepared by the inventive method3DMPaPhen is 10 in concentration-5Mol/L's
CH2Cl2Fluorescent exciting spectrogram in solution；
Fig. 5 is Rare Earth Europium Complex Eu (TTA) prepared by the inventive method3DMPaPhen is 10 in concentration-5Mol/L's
CH2Cl2Fluorescence emission spectrogram of compound in solution；
Fig. 6 is Rare Earth Europium Complex Eu (TTA) prepared by the inventive method3DMPaPhen and PET composite fibre, when dilute
Native luminescent material in the fibre content be 0.05% when, concentration is 10-5Mol/L DMF (Dimethyl Formamide, N.N-
Dimethylformamide) fluorescent exciting spectrogram in solution；
Fig. 7 is Rare Earth Europium Complex Eu (TTA) prepared by the inventive method3DMPaPhen and PET composite fibre, when dilute
Native luminescent material in the fibre content be 0.05% when, concentration is 10-5Fluorescence emission spectrogram of compound in mol/L DMF solution.
Wherein：
Abscissa Wavenumbers in Fig. 2 represents wave number；
Abscissa Wavelength represents wavelength in Fig. 4, Fig. 5, Fig. 6 and Fig. 7, and ordinate Intensity represents intensity.
Embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention
In accompanying drawing, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is
A part of embodiment of the present invention, rather than whole embodiments.Described in a kind of accompanying drawing or embodiment of the present invention
Element and the element that can be shown in one or more other accompanying drawings or embodiment of feature and feature be combined.Should
Note, for purposes of clarity, eliminated in accompanying drawing and explanation unrelated to the invention, known to persons of ordinary skill in the art
Part and the expression and description of processing.Based on the embodiment in the present invention, those of ordinary skill in the art are not paying creation
Property work under the premise of the every other embodiment that is obtained, belong to the scope of protection of the invention.
The present invention provides a kind of Europium complex luminescent material, and its chemical formula is C24H16EuN4SF3O2, molecular formula
For Eu (TTA)3DMPaPhen, wherein TTA are：α-thiophene trifluoro formyl acetone, DMPaPhen are：2,3- dimethyl pyrazines are simultaneously
[1,10] Phen, structural formula is：
The construction unit of complex is as follows：
Present invention simultaneously provides a kind of preparation method of Europium complex luminescent material, comprise the following steps：
(1) preparation of part 2,3- dimethyl pyrazines simultaneously [1,10] Phen：
A, 1,10- Phens and KBr be put into flask, it is 3 that volume ratio is added dropwise at -8 DEG C to -12 DEG C:1-2's
The mixed acid solution of the concentrated sulfuric acid and concentrated nitric acid, 0.5-1.5h is reacted at -8 DEG C to -12 DEG C, is heated to 75-95 DEG C of reaction 130-
150min；Reaction solution is instilled in ice cube, quick stirring, and pH is adjusted to 6-7 with NaOH, obtains neutralizing solution, with described in solvent extraction
Solution is neutralized, vacuum distillation obtains yellow product 5,6- diketone -1,10- Phens；
0.4-1g KBrs are added per 1g 1,10- Phens correspondence；
The mixed acid solution added per 1g1,10- Phens correspondence is 20-30ml；
The solvent of the extraction is dichloromethane or chloroform；
B, by 5,6- diketone -1,10- Phens, hydroxylamine hydrochloride and BaCO310- is reacted in 70-80 DEG C of ethanol
13h, distillation, solid is washed with 0.2-0.3mol/L watery hydrochloric acid, and suction filtration is washed for several times with the first mixed liquor, then is dried in vacuo,
Vacuum is 0.09MPa, and drying temperature is 60-90 DEG C；Drying time is 5-12h；Light yellow product 5,6- dioxime -1 is obtained,
10- Phens；
5,6- diketone -1,10- the Phens, hydroxylamine hydrochloride and BaCO3Mass ratio be 1:0.7-2:0.7-2；
40-60ml ethanol is added per 0.84g5,6- diketone -1,10- Phens correspondence, the reaction time is 10-13h；
First mixed liquor be ethanol or methanol in ethanol and ether or methanol and ether, first mixed liquor with
The volume ratio of ether is 1:2-6；
The first mixed liquor added per 0.84g5,6- diketone -1,10- Phens correspondence is 15-30ml；
C, 5,6- dioxime -1,10- Phens are put into absolute ethyl alcohol, obtain alcoholic solution, heated under inert gas shielding
To 70-80 DEG C, take sodium hydrosulfite to be dissolved in the ammonia spirit that content is 3%-5%, obtain the second mixed liquor, the second mixed liquor is added
Enter in above-mentioned alcoholic solution；The second mixed liquor with first time equivalent is added after 15-45min, and 1.5- is reacted at 75-85 DEG C
2h；Normal temperature is cooled to, suction filtration is washed for several times, vacuum drying for several times, then with ethanol or acetone with distillation water washing, and vacuum is
0.09MPa, drying temperature is 60-90 DEG C, and drying time is 4-10h；Obtain golden yellow 5,6- diamines -1,10- Phens；
5-10ml ethanol is correspondingly placed into per 1mmol 5,6- dioxime -1,10- Phens；
The mol ratio of the 5,6- dioximes -1,10- Phens and sodium hydrosulfite is 1：3-5；
It is dissolved in per 1mmol sodium hydrosulfites in the ammonia spirit that 0.6-1ml mass percent concentrations are 3%-5%；
2.5-4.5ml the second mixed liquor is added per 1mmol 5,6- dioxime -1,10- Phens correspondence；
D, 5,6- diamines -1,10- Phen and 3,4- diacetyl react to 10-13h at normal temperatures, vacuum distillation, Gu
Body is washed with the mixed liquor of methanol and water, vacuum drying, and vacuum is 0.09MPa, and drying temperature is 60-90 DEG C, drying time
For 5-12h；Obtain white powder 2,3- dimethyl pyrazines simultaneously [1,10] Phen；
The mass ratio of the 5,6- diamines -1,10- Phens and 3,4- diacetyl is 1.5-3：1；
The volume ratio of the methanol and water is 1:8-12；
The cumulative volume that methanol and water are added per 1g 5,6- diamines -1,10- Phens correspondence is 8-12ml.
(2) organic RE europium complex Eu (TTA)3The preparation of DMPaPhen luminescent materials：
By Eu2O3With concentrated hydrochloric acid mixing, Eu2O3Mass ratio with concentrated hydrochloric acid is 1:1-10, is evaporated on electric jacket, then
It is configured to ethanol solution；Take a certain amount of Phen neutral ligand DMPaPhen to be put into flask, be added dropwise at 55-60 DEG C and neighbour
The equimolar EuCl of phenanthroline neutral ligand DMPaPhen3Ethanol solution, stir 40-80 minutes；Phen is added dropwise neutral
Part DMPaPhen, the HTTA of 3 times of moles ethanol solution, adjust pH to 6-7, autoclave are transferred to, in 120-160 with triethylamine
At DEG C, setting pressure is less than 10MPa, more than 0.110MPa, insulation reaction 5-10h；Pressure is more than 0.1MPa, and vacuum distillation is cold
But solid, suction filtration are separated out, alcohol is washed for several times, washed several times with water, are dried in vacuo, vacuum is 0.09MPa, drying temperature is 60-90 DEG C,
Drying time is 8-12h；Obtain nano level blush powder.
The present invention also provides a kind of preparation method of Europium luminous polyester fiber, and usage right requires organic dilute described in 1
Native europium complex luminescent material and PET (polyethylene terephthalate, pet resin)
Carry out composite spinning.
The preparation process of the Europium luminous polyester fiber of the present invention is divided into two parts completion, and rare-earth europium is prepared first and is lighted
Material, is then prepared into rare earth luminous PET color master batch with PET master batch, then is cut into slices melt spinning with PET.Obtain in ultraviolet lighting
The Europium luminous polyester fiber of pure feux rouges can be launched by penetrating down.
Specifically include following steps：
(1) Europium complex luminescent material and PET master batch are sufficiently mixed, prepared using screw extruder
Go out Masterbatch, be dried in vacuo, its moisture content is less than 20ppm；Europium complex luminescent material accounts for Masterbatch gross mass
0.3%-30%.The Masterbatch prepared is using vacuum drying, and its vacuum ＜ 0.095MPa, the temperature of drying are
100-140 DEG C, dry time be 10-16h.
(2) Masterbatch is uniformly mixed by a certain percentage with dried PET sections, the Masterbatch is cut with PET
The weight ratio of piece is 1:20-100, makes organic RE europium complex Eu (TTA)3DMPaPhen content is 0.05-5%；In spy
Determine under spinning process condition, through screw rod melt extruded, filtering, static mixing, spinneret, slow cooling, drawing-off and package, prepare compound
Luminescent fibre；
The present invention makes its triplet and rare earth Eu by preparing a Phen neutral ligand3+Energy level phase
Match somebody with somebody so that prepared new complexes ultraviolet light or it is electroluminescent under the conditions of have efficient, luminous intensity it is high,
Launch pure feux rouges, the Europium complex luminescent material that heat endurance is good, grain diameter is small.
The present invention by using melt spinning method, prepare luminous intensity it is high, launch it is pure
Luminous polyester fiber.Under ultraviolet light, luminous polyester fiber launches pure feux rouges at 615nm.
The present invention provides a kind of Europium luminous polyester fiber again, is prepared according to above-mentioned preparation method.
The present invention is prepared for a kind of Phen neutral ligand and combines α-thiophene trifluoro formyl acetone and rare earth Eu (III)
It is coordinated, is titrated using first normal pressure, the method for rear reaction under high pressure prepares the Rare Earth Europium Complex Eu close to nanoscale
(TTA)3DMPaPhen luminescent materials.The material is 10 in concentration-5Mol/L CH2Cl2Launch very strong in solution, at 615nm
Pure feux rouges.Composite molten spinning is carried out as luminescent material and polyethylene terephthalate (PET) using this complex
Prepare luminescent fibre.It is 10 in concentration when content is 0.05% to rare earth luminescent material in the fibre-5Mol/L DMF solution
In launch stronger pure feux rouges, luminous position is still at 615nm.The luminescent fibre is that a kind of excitation is high, spinnability is preferable
Luminescent fibre.
The present invention prepare it is efficient, color is pure, stability good, particle diameter be nano level organic RE light material
Material has practical significance applied to the efficient, luminescent fibre of good spinnability is prepared.
The Orgnic RE complex Eu (TTA) of the present invention3Recombination luminescence fiber prepared by DMPaPhen and PET, the fibre
Dimension is nontoxic, without radiocontamination, it is processed after can the false proof of high-grade goods, lighting clothes, seabed operation, molecular probe,
The fields such as biochip, communication, solar cell have important application.
Luminescent fibre prepared by the embodiment of the present invention, Europium luminescent material used is Eu (TTA)3DMPaPhen, high polymer material is PET.Below by specific embodiment, the present invention is described further.
Embodiment 1
Rare Earth Europium Complex Eu (TTA)3DMPaPhen preparation process is as follows：
The synthesis of 1,10- Phen -5,6- diketone (compound 1)：1g 1,10- Phens and 0.6g are weighed respectively
KBr is added in 100mL two mouthfuls of flasks, and flask is put into ice salt bath and is cooled to -10 DEG C.The 16mL concentrated sulfuric acids are measured to pour into
In 200mL beaker, 8ml concentrated nitric acids are then measured with graduated cylinder.It is slowly dense toward being added dropwise in beaker with dropper under the conditions of the ice salt bath
Nitric acid, is added dropwise while being stirred with glass bar, dropwise addition about takes 30min or so, can be smoldered if dropwise addition is too fast.Acid solution is prepared
After start slowly to be added dropwise into flask, dropwise addition process is maintained under -10 DEG C of condition of ice bath, and 0.5h or so is about added dropwise.Then ice
Bath reaction 1h and then temperature programming are to 85 DEG C, and insulation reaction 130min, reaction is cooled to normal temperature after terminating.Separately take a 500ml's
Beaker is put into ice bath, the ice cube then frozen in advance toward input in beaker, and reacted solution is slowly added drop-wise on ice cube,
Drip while stirring of exerting oneself.Weigh moment holding system in 30g or so NaOH wiring solution-formings, neutralization reaction liquid, N-process
Inside have ice, and firmly stir, about 1h or so is neutralized and finished, neutralize to pH value 6-7 or so, stirring three minutes to pH value not
Become.Use CH2Cl2Extraction neutralizes solution, and anhydrous magnesium sulfate dries extract, and then distillation extraction liquid, obtains yellow powder, then
Needle-like yellow product 0.942g is obtained with ethyl alcohol recrystallization, yield is：94.2%, m.p=251-252 DEG C,1H NMR
(400MHz,CDCl3):δ 9.14 (d, J=4.6Hz, 2H), 8.52 (d, J=7.9Hz, 2H), 7.61 (dd, J=7.7,4.7Hz,
2H).IR(KBr):3062,1685,1577,1562,1461,1413,1317,1294,1207,1116,1010,925,808cm-1。
The synthesis of 1,10- Phen -5,6- dioximes (compound 2)：0.84g chemical combination is added into 100mL single-necked flasks
Thing 1,1.18g barium carbonates and the dried hydroxylamine hydrochlorides of 1.2g, then add 60ml absolute ethyl alcohols.Heating is begun to warm up, is heated up
Continue to react 12h to backflow, stop reaction, reaction unit, which is made into distilling apparatus, carries out vacuum distillation.Take 12mol/L dense salt
Sour 4.16mL, is made into 0.25mol/L watery hydrochloric acid, and the hydrochloric acid for measuring 20mL preparations is poured into flask, and stirring at normal temperature 30min is laggard
Row suction filtration.Filter cake methanol and ether 1:5 mixed liquor 20ml washs three times and then vacuum drying, and vacuum is 0.9MPA, does
Dry temperature is 65 DEG C；Drying time is 10h；Finally obtain product as light yellow solid 0.76g, yield 90.4%, m.p=235-236
℃。
The preparation of 5,6- diamines -1,10- Phens (compound 3)：By 6mmol 5,6- dioxime -1,10- Phens
40ml absolute ethyl alcohols are put into, obtain being heated to 75 DEG C under alcoholic solution, inert gas shielding, takes 25mmol sodium hydrosulfites to be dissolved in 20ml and contains
Measure in the ammonia spirit for 5%, obtain the second mixed liquor, quickly add the mixed liquors of 20ml second in above-mentioned alcoholic solution.45min
See afterwards and the same mixed liquors of above-mentioned 20ml second are added when yellow solid matter is separated out, and 2h is reacted at 80 DEG C.It is cooled to often
Temperature, suction filtration wash 3 times, vacuum drying, vacuum is 0.09MPa, and drying temperature is 65 with distillation water washing 3 times, then with ethanol
℃；Drying time is 5h；Obtain bright yellow solid product, yield 76.0%, m.p>350℃,1HNMR(400MHz,DMSO):δ
8.76(m,2H),8.60(m,2H),7.58(m,2H),5.31(s,4H).IR(KBr):3371,3263,2594,1654,1608,
1566,1483,1460,1433,1410,1349,1303,1280,1123,1074,1006,799,650,624,478。
The synthesis of 2,3- dimethyl pyrazines simultaneously [2,3-f] [1,10] ferrosin (DMPaPhen)：Weigh 0.52g compounds 3
In the flask for adding 150ml, 75mL absolute ethyl alcohols are added.0.21g 3 is measured, 4- diacetyl is made into 10mL ethanol solutions, normal temperature
Descend to be slowly added dropwise after 3,4- diacetyl, completion of dropwise addition into three-necked flask and continue normal-temperature reaction, stop after reaction 12h.Then subtract
Pressure evaporates solvent, and solid product pours into 11ml (methanol：Water=1:10) washed, then filtered in solution, filter cake
Silica gel is admixed after drying and carried out post separation；First use petroleum ether：Ethyl acetate=3:1 crosses post, then tunes up polarity ethyl acetate：
Methanol=5:1.Eluent decompression is evaporated, and solid is recrystallized again, is dried in vacuum overnight at 75 DEG C, final to obtain product as white needles
0.47g, yield is：64.4%, m.p=281-282 DEG C,1H NMR(400MHz,CDCl3):δ 9.49 (t, J=27.1Hz,
2H), (s, the 6H) .IR (KBr) of 9.36 (m, 2H), 7.81 (dd, J=7.9,4.4Hz, 2H), 2.87:3417,1573,1513,
1463,1421,1388,1342,1253,1213,1177,1121,1074,1010,979,816,744,713,693,637,
572,445。
Complex Eu (TTA)3DMPaPhen synthesis：0.67g α-thiophene trifluoro formyl acetone is added into three-necked flask,
20ml absolute ethyl alcohols, are stirred and heated to 60 DEG C.The ethanol solution of the Europium chloride prepared is slowly added dropwise.Then it is added dropwise NaOH's
Ethanol solution, adjusts pH to 6-7, and neutralization terminates rear insulation reaction 1h.Weigh 0.26g DMPaPhen and be dissolved in 20ml absolute ethyl alcohols
In, slowly it is added dropwise in flask, after completion of dropwise addition, solution point is picked with glass bar and observes transmitting under uviol lamp to filter paper
Go out very strong feux rouges.Regulation pH value is 6-7, is then transferred in autoclave, at 140 DEG C, control pressure is 1MP, is incubated
React 6h, reaction, which terminates rear solvent concentration, has white solid precipitation to 15ml or so.It is cooled to after room temperature and carries out suction filtration, filter cake is first
Washed 3 times, then be washed with deionized three times with absolute ethyl alcohol.Then ethyl alcohol recrystallization is used, vacuum is 0.09MPa, 70
DEG C vacuum drying 8h, obtain blush powder 0.79g.Yield：71.3%.M.p=279-281 DEG C.
The infrared spectrum of complex such as Fig. 1：The characteristic absorption peak ν of part α-thiophene trifluoro formyl acetone (HTTA)C=O
(1656cm-1) 1625cm is moved to after coordination-1Place.HTTA parts, respectively in 1305cm after coordination-1And 1142cm-1Place goes out
Existing νas(CF3)And νS(CF3)Characteristic absorption peak.And νC=C(thiphene ring) and νC-HThe characteristic absorption peak of (thiphene ring) exists respectively
1353cm-1And 1061cm-1Place occurs.νC-SCharacteristic peak appear in 722cm-1, these absolutely prove α-thiophene trifluoro formyl third
Ketone is coordinated successfully.For DMPaPhen parts after coordination its C=N stretching vibration red shift to 1478cm-1.In addition
561cm-1One absworption peak at place is N-Eu absworption peak, and these results confirm that DMPaPhen is coordinated.The nuclear-magnetism number of complex
According to：1HNMR(400MHz,CDCl3):δ 11.66 (s, 2H), 11.39 (s, 2H), 10.2 (s, 2H), 6.99 (d, J=4.4Hz,
3H), 6.51 (s, 3H), 6.05 (d, J=75.2Hz, 3H), 3.25-2.64 (m, TTA-3H, CH3-6H).In elementary analysis bracket
For theoretical value：Anal.calcd.C:44.58(44.66),H:2.17(2.25),N:5.10(5.21).
Fig. 4 is that complex is 10 in concentration-5Mol/L CH2Cl2Fluorescent exciting spectrogram in solution, complex exists
Wider bands of a spectrum, a length of 373nm of optimum excitation wave are presented between 260nm-420nm.
Fig. 5 is that complex is 10 in concentration-5Mol/L CH2Cl2Fluorescent exciting spectrogram in solution from emission spectrum,
Complex occurs in that Eu at 590nm (orange red photochromic), 615nm (pure feux rouges) and 651nm3+Characteristic emission peak, and half-peak breadth
Degree is narrower.Emission peak at wherein 590nm and 615nm is europium (III) respectively5D0→7F1Transition and5D0→7F2Transition.615nm
Place's very strong spike is far longer than other peaks at two, illustrates that complex has very strong monochromaticjty.From fluorescence spectra emission light
Intensity finds out that DMPaPhen parts show very outstanding " collaboration " effect after being coordinated with Eu (III), there is very strong at 615nm
Spike, it is a kind of good red illuminating material to illustrate made complex.
The preparation of the luminous PET of ultraviolet light, its process is as follows：
The nanoscale luminescent material of above-mentioned preparation is sufficiently mixed with PET master batch, prepared using double screw extruder
Go out the Masterbatch containing organic rare-earth ligand 5%, vacuum (vacuum is 0.09MPa), drying 12h at 115 DEG C makes its moisture content
Less than 20ppm.
By PET polyester chip transportations into pre-crystallizer, pre-crystallization temperature is set as 170-175 DEG C, during pre-crystallized stop
Between 15-20min.Continuously be transported to main drying tower again by the material of pre-crystallizer, set main drying tower drying temperature as
166-170 DEG C, 6h is dried in main drying tower.
Dried material feeds single screw extrusion machine, the feed quantity of masterbatch simultaneously with the masterbatch with rare earth luminescent material
Control is in make rare earth luminescent material account for whole inventory 0.05%.Screw rod is through variable frequency regulating speed control melt outlet pressure.
Material after Screw Extrusion makes melt mixed uniform through static mixer, is then dispensed for spinning manifold, and setting is spun
Silk spin manifold temperature is 275-285 DEG C；Blend melt carries out spinneret through spinneret.
Cross air blasting is cooled and shaped, setting cross air blasting humidity 65%, wind speed 0.40-0.5m/s.Carried out after being oiled again through oil nozzle
High-speed winding, is made POY luminous polyester fibers.
Fig. 6 be rare earth luminescent material in the fibre content be 0.05% when, concentration be 10-5In mol/L DMF solution
Fluorescent exciting spectrogram.Wider bands of a spectrum, a length of 343nm of optimum excitation wave are presented in composite fibre between 250-378nm.
Fig. 7 be rare earth luminescent material in the fibre content be 0.05% when, concentration be 10-5In mol/L DMF solution
Fluorescence emission spectrogram of compound.The fluorescence emission spectrum of composite fibre is mainly reflected in the characteristic emission (590nm (orange light) of Eu (III)
With 615nm (pure feux rouges)).The position of emission peak does not change in composite fibre, and is still in narrow emission, explanation
Prepared composite fibre has very high excitation.
Embodiment 2
The preparation of luminescent material of the present embodiment only to different content and the luminescent fibre under different spinning process conditions is entered
Row explanation, the preparation method be the same as Example 1 of its luminescent material, the preparation process of luminescent fibre is as follows：
The nanoscale luminescent material of above-mentioned preparation is sufficiently mixed with PET master batch, prepared using double screw extruder
Go out the Masterbatch containing organic rare-earth ligand 5%, vacuum (vacuum is 0.09MPa), drying 12h at 120 DEG C makes its moisture content
Less than 20ppm.
By PET polyester chip transportations into pre-crystallizer, pre-crystallization temperature is set as 170-175 DEG C, preferably 175 DEG C, in advance
Crystallize residence time 17-23min, preferably 23min.Main drying tower is continuously transported to again by the material of pre-crystallizer, is set
Main drying tower drying temperature is 165-170 DEG C, and preferably 165 DEG C, 6.5h is dried in main drying tower.
Dried (PET) material feeds single screw extrusion machine, masterbatch simultaneously with the Masterbatch with rare earth luminescent material
Fed by metering valve, its content is controlled in make rare earth luminescent material account for whole inventory 0.3%.Screw rod is through frequency control control
Melt outlet pressure processed.
Material after Screw Extrusion makes melt mixed uniform through static mixer, is then dispensed for spinning manifold, and setting is spun
Silk spin manifold temperature is 270-285 DEG C, preferably 285 DEG C；Blend melt carries out spinneret through spinneret.
Cross air blasting is cooled and shaped, setting cross air blasting humidity 65%, wind speed 0.40-0.45m/s；Carried out after being oiled again through oil nozzle
Low-speed rolling is around obtained UDY luminous polyester fibers.
Embodiment 3
A kind of preparation method of Europium complex luminescent material, comprises the following steps：
(1) preparation of part 2,3- dimethyl pyrazines simultaneously [1,10] Phen：
A, by mass ratio be 1:11,10- Phens and KBr is put into flask, and it is 3 that volume ratio is added dropwise at -8 DEG C:
1 concentrated sulfuric acid and the mixed acid solution of concentrated nitric acid, per 1g 1, the mixed acid solution that 10- Phens correspondence is added is 25ml；At -8 DEG C
Lower reaction 1.5h, is heated to 90 DEG C of reaction 120min；Reaction solution is instilled in ice cube, quick stirring, is adjusted pH to 6-7 with NaOH, is obtained
To mixed solution, with mixed solution described in chloroform extraction, vacuum distillation obtains yellow product 5,6- diketone -1,10- neighbour's Féraud
Quinoline；
B, by mass ratio be 1:2:1 5,6- diketone -1,10- Phens, hydroxylamine hydrochloride and BaCO3In 70 DEG C of ethanol
Middle reaction 3h, per 0.84g 5, it is 40ml that 6- diketone -1,10- Phen correspondence, which adds ethanol,；Distillation, solid 15ml,
0.2mol/L watery hydrochloric acid washing, suction filtration is washed for several times with the first mixed liquor, and first mixed liquor is ethanol and ether, institute
The volume ratio for stating the ethanol in the first mixed liquor and ether is 1:6；Add per 0.84g 5,6- diketone -1,10- Phens correspondence
The first mixed liquor entered is 15ml；It is dried in vacuo again, vacuum is 0.09MPa, drying temperature is 75 DEG C；Drying time is 8h；
Obtain light yellow product 5,6- dioxime -1,10- Phens；
C, 5,6- dioxime -1,10- Phens are put into absolute ethyl alcohol, per 1mmol 5,6- dioxime -1,10- Phens
It is correspondingly placed into 10ml ethanol；Obtain being heated to 80 DEG C under alcoholic solution, inert gas shielding, take 5,6- dioxime -1,10- Phens
The sodium hydrosulfite of 5 times of moles is dissolved in the ammonia spirit that content is 3%, obtains the second mixed liquor, and the second mixed liquor is added
State in alcoholic solution；The second mixed liquor with first time equivalent is added after 30min, and 1.5h is reacted at 79 DEG C；It is cooled to normal temperature,
Suction filtration, is washed for several times, vacuum drying, vacuum is 0.09MPa, and drying temperature is 70 for several times, then with acetone with distillation water washing
DEG C, drying time is 6h；Obtain golden yellow 5,6- diamines -1,10- Phens；
The ammonia spirit that 0.75ml mass percent concentrations are 3% is dissolved in per 1mmol sodium hydrosulfites；
3ml the second mixed liquor is added per 1mmol 5,6- dioxime -1,10- Phens correspondence；
D, by mass ratio be 3：15,6- diamines -1,10- Phen and 3,4- diacetyl reacts 13h at normal temperatures, subtracts
Pressure distillation, solid is washed with the mixed liquor of methanol and water, and the volume ratio of methanol and water is 1:8, it is dried in vacuo, vacuum is
0.09MPa, drying temperature is 75 DEG C, and drying time is 10h；Obtain white powder 2,3- dimethyl pyrazines simultaneously [1,10] adjacent Féraud
Quinoline；
The cumulative volume 11ml of methanol and water is added per 1g 5,6- diamines -1,10- Phens correspondence.
(2) organic RE europium complex Eu (TTA)3The preparation of DMPaPhen luminescent materials：
It is 1 by mass ratio:10 Eu2O3With concentrated hydrochloric acid mixing, it is evaporated on electric jacket, is then configured to ethanol solution；Take
A certain amount of Phen neutral ligand DMPaPhen is put into flask, is added dropwise and Phen neutral ligand at 60 DEG C
The equimolar EuCl of DMPaPhen3Ethanol solution, stir 40 minutes；Be added dropwise Phen neutral ligand DMPaPhen, 3 times rub
The HTTA of your amount ethanol solution, adjusts pH to 6-7, is transferred to autoclave with triethylamine, at 120 DEG C, and Stress control is protected in 2MP
Temperature reaction 10h；Vacuum distillation, cooling separates out solid, and suction filtration, alcohol is washed for several times, washed several times with water, is dried in vacuo 8h at 80 DEG C, obtains
Nano level blush powder.
The preparation method of Europium luminous polyester fiber：
Specifically include following steps：
(1) Europium complex luminescent material and PET master batch are sufficiently mixed, prepared using screw extruder
Go out Masterbatch, be dried in vacuo, its moisture content is less than 20ppm；Europium complex luminescent material accounts for Masterbatch gross mass
10%.Prepare the vacuum ＜ 0.095MPA used after Masterbatch, the temperature of drying is for 115 DEG C, dry time
16h。
(2) Masterbatch is uniformly mixed by a certain percentage with dried PET sections, the Masterbatch is cut with PET
The weight ratio of piece is 1:20, make organic RE europium complex Eu (TTA)3DMPaPhen content is 0.5%；In specific spinning work
Under the conditions of skill, melt extruded, filtering, static mixing are squeezed through screw rod, spinning manifold is then dispensed for, spinning body temperature is set
280℃；Blend melt carries out spinneret through spinneret.Cross air blasting is cooled and shaped, setting cross air blasting humidity 70%, wind speed 0.40m/s；
Low-speed rolling is carried out after being oiled again through oil nozzle around obtained UDY luminous polyester fibers.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
The present invention is described in detail with reference to the foregoing embodiments, it will be understood by those within the art that：It still may be used
To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic；
And these modification or replace, do not make appropriate technical solution essence depart from various embodiments of the present invention technical scheme spirit and
Scope.
Claims (9)
1. a kind of preparation method of Europium complex luminescent material, it is characterised in that comprise the following steps：
(1) preparation of part 2,3- dimethyl pyrazines simultaneously [1,10] Phen：
A, 1,10- Phens and KBr be put into flask, it is 3 that volume ratio is added dropwise at -8 DEG C to -12 DEG C:1-2 dense sulphur
The mixed acid solution of acid and concentrated nitric acid, 0.5-1.5h is reacted at -8 DEG C to -12 DEG C, is heated to 75-95 DEG C of reaction 130-150min；
Reaction solution is instilled in ice cube, quick stirring, and pH is adjusted to 6-7 with NaOH, obtains neutralizing solution, molten with being neutralized described in solvent extraction
Liquid, vacuum distillation obtains yellow product 5,6- diketone -1,10- Phens；
B, by 5,6- diketone -1,10- Phens, hydroxylamine hydrochloride and BaCO310-13h is reacted in 70-80 DEG C of ethanol, is steamed
Evaporate, solid is washed with 0.2-0.3mol/L watery hydrochloric acid, suction filtration, washed for several times with the first mixed liquor, then be dried in vacuo, obtain shallow
Yellow product 5,6- dioxime -1,10- Phens；
C, 5,6- dioxime -1,10- Phens are put into absolute ethyl alcohol, obtain being heated to 70- under alcoholic solution, inert gas shielding
80 DEG C, take sodium hydrosulfite to be dissolved in the ammonia spirit that mass percent concentration is 3%-5%, obtain the second mixed liquor, second is mixed
Liquid is closed to add in above-mentioned alcoholic solution；The second mixed liquor with first time equivalent is added after 15-45min, and is reacted at 75-85 DEG C
1.5-2h；Normal temperature is cooled to, suction filtration is washed for several times for several times, then with ethanol or acetone with distillation water washing, and vacuum drying is obtained
Golden yellow 5,6- diamines -1,10- Phens；
D, 5,6- diamines -1,10- Phen and 3,4- diacetyl react to 10-13h at normal temperatures, vacuum distillation, solid is used
The mixed liquor washing of methanol and water, vacuum drying obtains white powder 2,3- dimethyl pyrazines simultaneously [1,10] Phen；
(2) organic RE europium complex Eu (TTA)3The preparation of DMPaPhen luminescent materials：
By Eu2O3With concentrated hydrochloric acid mixing, it is evaporated on electric jacket, is then configured to ethanol solution；Take a certain amount of Phen neutral
Part DMPaPhen is put into flask, is added dropwise and the equimolar EuCl of Phen neutral ligand DMPaPhen at 55-60 DEG C3
Ethanol solution, stir 40-80 minutes；Be added dropwise Phen neutral ligand DMPaPhen, the HTTA of 3 times of moles ethanol it is molten
Liquid, adjusts pH to 6-7, is transferred to autoclave, insulation reaction 5-10h with triethylamine；Vacuum distillation, cooling separates out solid, and suction filtration, alcohol is washed
For several times, washed several times with water, vacuum drying, obtains nano level blush powder；
The chemical formula of Europium complex luminescent material is C24H16EuN4SF3O2, molecular formula is Eu (TTA)3DMPaPhen,
Wherein TTA is：α-thiophene trifluoro formyl acetone, DMPaPhen are：2,3- dimethyl pyrazines simultaneously [1,10] Phen, structural formula
For：
2. the preparation method of Europium complex luminescent material according to claim 1, it is characterised in that：
In the step a：
0.4-1g KBrs are added per 1g 1,10- Phens correspondence；
The mixed acid solution added per 1g 1,10- Phens correspondence is 20-30ml；
The solvent of the extraction is dichloromethane or chloroform；
In the step b：
5,6- diketone -1,10- the Phens, hydroxylamine hydrochloride and BaCO3Mass ratio be 1:0.7-2:0.7-2；
40-60ml ethanol synthesis 8-13h is added per 0.84g 5,6- diketone -1,10- Phens correspondence；
First mixed liquor is the ethanol or methanol and ether in ethanol and ether or methanol and ether, first mixed liquor
Volume ratio be 1:2-8；
The first mixed liquor added per 0.84g 5,6- diketone -1,10- Phens correspondence is 15-30ml；
In the step c：
5-10ml ethanol is correspondingly placed into per 1mmol 5,6- dioxime -1,10- Phens；
The mol ratio of the 5,6- dioximes -1,10- Phens and sodium hydrosulfite is 1：3-5；
It is dissolved in per 1mmol sodium hydrosulfites in the ammonia spirit that 0.6-1ml mass percent concentrations are 3%-5%；
2.5-4.5ml the second mixed liquor is added per 1mmol 5,6- dioxime -1,10- Phens correspondence；
In the step d：
The mass ratio of the 5,6- diamines -1,10- Phens and 3,4- diacetyl is 1.5-3：1；
The volume ratio of the methanol and water is 1:8-12；
The cumulative volume that methanol and water are added per 1g 5,6- diamines -1,10- Phens correspondence is 8-12ml；
In the step (2)：
The Eu2O3Mass ratio with concentrated hydrochloric acid is 1:1-10.
3. the preparation method of Europium complex luminescent material according to claim 1, it is characterised in that：
In described step b, c, d and step (2)：Used vacuum is 0.09MPa, and drying temperature is 60-90 DEG C；Institute
It is 5-12h to state the drying time in step b；
Drying time in the step c is 4-10h；
Drying time in the step d is 5-12h；
Drying time in the step (2) is 5-12h；
The autoclave insulation reaction temperature is 120-160 DEG C, and pressure is less than 10MPa.
4. a kind of preparation method of Europium luminous polyester fiber, it is characterised in that usage right requires prepared by 1 methods described
Europium complex luminescent material is blended with PET sections, then luminous polyester fiber is made through melt spinning, and PET is poly- pair
PET resin.
5. the preparation method of Europium luminous polyester fiber according to claim 4, it is characterised in that：Specifically include following
Step：
(1) Europium complex luminescent material and PET master batch are sufficiently mixed, prepared using screw extruder outstanding
Master batch, vacuum drying makes its moisture content be less than 20ppm；
(2) Masterbatch is uniformly mixed by a certain percentage with dried PET sections, makes organic RE europium complex Eu
(TTA)3DMPaPhen content is 0.05-5%；Under spinning process condition, through screw rod melt extruded, filtering, static mixing,
Spinneret, slow cooling, drawing-off and package, prepare recombination luminescence fiber.
6. the preparation method of Europium luminous polyester fiber according to claim 4, it is characterised in that：
The Europium complex luminescent material accounts for the 0.3%-30% of Masterbatch gross mass.
7. the preparation method of Europium luminous polyester fiber according to claim 4, it is characterised in that：
The Masterbatch is 1 with the weight ratio that PET cuts into slices:20-100.
8. the preparation method of Europium luminous polyester fiber according to claim 4, it is characterised in that：It is described to prepare remarkably
The vacuum ＜ 0.095MPa that are used after master batch, the temperature of drying for 100-140 DEG C, time for drying be 10-16h.
9. a kind of Europium luminous polyester fiber, it is characterised in that：According to the preparation method system described in claim any one of 4-8
It is standby to obtain.
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| CN106699784B (en) * | 2017-01-10 | 2019-06-11 | 渤海大学 | The preparation method of the europium complex of thienyl-containing group and its application in terms of mercury ion sensing material |
| CN107418555B (en) * | 2017-03-27 | 2020-06-05 | 江苏弘盛新材料股份有限公司 | Preparation method and system of organic rare earth europium luminescent chinlon 6 slice |
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